Methods for making shaped articles



Jan. 10, 1956 L. TlTUS ETAL 2,729,355

METHODS FOR MAKING SHAPED ARTICLES Filed Oct. 16, 1952 ALUMINUM HYDRA FE INVENTORS LESLIE TIT WILLIAM F. VAN LOE N ATTORNEY pockets.

forth.

United S a s P wO' 2,729,855 METHODS FOR MAKING SHAPED ARTICLES Leslie Titus, Campbell, Calif., and William F. Van Loenen, Baton Rouge, La., assignors to Kaiser Aluminum &

. Chemical Corporation, Oakland, Calif., a corporation of Delaware Application October 16, 1952, Serial No. 315,122

.8 Claims. (CI. 18-55) This invention relates to novel methods or processes for obtaining shaped bodies of alumina and hydrated alumina containingmaterials and to, the novel articles or products resulting therefrom. More particularly, this invention relates to a method of briquetting particulate hydrated alumina containing material in briquetting apparatus without the use of special binders and/or lubricants. Specifically, the hereinafter described invention relates to a method of substantially increasing the output of roll type briquetting machines when particulate hydrated alumina is briquetted therein without the use of binders and/ or lubricants mixed with the hydrate or lubricants added to siderable amount of recycle is necessary due to the amount .of. broken briquettes obtained. This is believed caused by the hydrate sticking in the die pockets giving rise, after compression, to a shearing stress being placed on the briquettes on release of the rolls and their dies. Moreover, the pocketsclog up and are thereafter ineffective in producing briquettes on the next cycle of the rolls and in some cases the material must be chiseled from the die It is not uncommon to have better than 50% of the briquettes broken when briquetting hydrated alumina without the aid of binders and/or lubricants. Even with binders and lubricants, the yield of unbroken briquettes of requisite strength is low. Since the pieces of broken briquettes as well as normal amounts of lands and granules of lines from incomplete briquetting must be recycled in order to utilize the full supply of material, the need for overcoming this sticking and clogging of the rolls is apparentfor the purposeof increasing the through put of the apparatus. Increased strengths are requisite for subsequent handling before and after calcination for use in the preparation of aluminum fluoride, the control of dust losses, to support beds of sufficient depth, and so Accordingly, it is a primary object of the herein described invention to provide a method of producing shaped alumina and hydrated alumina containing materials with an increase in the number of whole briquettes formed as well as an increase in the strength thereof.

It is another object of the herein described invention -to provide a method for increasing the output of roll type necessary to use them.

It is yet another object of this invention to provide a "method for producing calcined alumina containing brir 2,129,855 Patented Jan. 10, 195d quettes having increased strength with an increase in the number of whole briquettes obtained.

It is a further object of this invention to provide a method for obtaining alumina containing briquettes especially useful for the production of aluminum fluoride.

It is a still further object of the present invention to provide novel alumina hydrate containing briquettes.

It is again an object of this invention to provide novel alumina containing briquettes.

It is yet again an object of this invention to provide alumina containing briquettes especially suitable in the production of aluminum fluoride.

These and other objects and advantages of the present invention will become more apparent from the following detailed description, examples, and drawing, wherein:

Figure l is a schematic diagram of an arrangement of apparatus for briquetting hydrated alumina, and

Figure 2 is a top plan view of a portion of the apparatus shown in Figure 1 showing the location of the die pockets according to some types of briquetting apparatus.

1 It has now been discovered according to the present invention that shaped bodies can easily be produced from a mass of particulate hydrated alumina containing material by providing a film or layer of a volatile liquid on the pressing surfaces entering the compression zone, feeding hydrate to said zone in amount sufiicient to establish a pressure on the material to briquet the same, maintaining a temperature above the atmospheric: boiling point of the liquid in the compression zone, and thereafter releasing the pressure on the pressing surfaces so that the liquid volatilizes, that is vaporizes or flashes at atmospheric pressure, thus materially aiding in discharging the briquettes from the dies. This method essentially completely eliminates clogging of the dies and greatly reduces the incidence of broken pellets so that the production of whole bodies is almost and material recirculation is minimized. The method is further characterized by providing bodies of greatly increased breaking strengths before and after calcination.

The establishing and maintaining of a temperature above the atmospheric boiling point of the volatile liquid in the compression zone may be accomplished solely from the heat generated by the pressure or the latter may be supplemented by heat input.

Such additional heat it supplied to the pressing or compression zone, can readily be furnished in a number of ways. For example, the heat may be obtained by heating the dies or rolls of the briquetting apparatus by means of pipes and so forth carrying heated water or gas adjacent. or in heat exchange relationship with, the surfaces of the rolls. Another method is to supply water at an elevated temperature to the rolls. Still another method at present preferred is to heat the hydrate or furnish hydrate already heated by the driers used in removing the free water from the precipitated hydrate. Combinations of any of the foregoing techniques may be employed.

It, of course, will be understood that in many instances sufi'icient heat will be generated by the pressure developed during formation of briquettes as a result of friction, compression, etc., to provide the increase in temperature requisite for flashing after compression. Such generation of heat is accomplished by subjecting the hydrate feed to pressures sufficient to raise the temperature above the boiling point of the liquid. If the temperature rises too high so that a film of volatile liquid will not remain on the roll surfaces, the rolls can be cooled by supplying water to the surfaces thereof by means of a dip pan or additional sprays or the temperature of the feed reduced if .it is supplied heated. It is only necessary that the temperature of the pressing surfaces entering the compression zone be maintained such that the liquid film exists and that sufiicient heat be available during compressteps. contain residual amounts of silica, sodium aluminate or sion in said zone to effect an increase in temperature so that on release of pressure from the die surfaces the liquid will flash at atmospheric pressure.

ln cesenof water as the liquid,,t he hydrate may be fed to" the rolls at temperatures less than about 212" F. as the heat generated during compression will cause flashrel ase fPF S B urth th .f ,,m ,be a higher t'emperature,"up toabout 350 F. althoughinereajsedfamounts of water may be necessary to cool the roll slurface's tomaintain the necessary film. However, it iepre'ferable that the resultant temperature of the hydrate f'e'dand the wetted rolls be at about 200 F. upon enteri ng the compression zone. Further, a feed which is h"'ted tendsto flow better through the hopper to the dies and'thus facilitates operations. In any case, it isipr'eferred to soregulate the feed temperature and amount of ,o'rithe rolls that the liquidfilm on the rolls enter- 'ing the 'cornpressionzone is just below the boiling point The hydrated alumina containing material herein disclosed is definedto meanjin'thespecificatmn and claims ha, alurniria hydrate in anyof its various forms,

an mixturesof alumina andalumina hydrate, partially hydrated or partiallydehydrated aluminal The material tr "tedl ispredominantly hydrated alumina andhas the ch rac'teristics thereof. In addition, in 'its calcined form, 'the'allimina containing material, may contain various ainounts of residual water, etc., depending on' time and era ture of calcination as is well known in the art. The alumina andhydrated alumina containing materials jrnay a lso contain, minor amounts of impurities or adventiitioujsimaterials which do not adversely affect the propof'the resultingarticles, and, it, of course, is within the purview of this invention that such materials may alsdcontain minor amounts of catalysts as'well as mate- 'rials promote the catalytic activity of the alumina amr/ or hydrate.

Likewise, lubricants and binders maybe present, but n.

leads to less satisfactory results, and in some cases is det- "rirnental such as producing sticking inthe dies, or brittlemess and spalling'of the pellets. Accordingly, it is an'advantage of the present invention that customarybinders "of" lubricants are avoided While achieving the new and tinexpee'ted results here'indisclosed, elimination of sticking'and breakage. 'In addition, the use of such binders or"'liibricants" complicates the process by adding extra The alumina hydrate containing feed may also "the drier's or 'by pickup from the atmosphere during storage or between the'driersand pressing station. They Hydrated alumina containing material is used in particulate form, that is coarse'to very fine or pulverulent particle size. For most pu'rposes, it is best to usea mixture of sizes ranging from coarse to very fine. Further, theuse of'th eterrn briquetting is defined to rneanalso pelleting,

p'illi'rig', tabletting, andso forth. The preferred volatile liquid is water, because of econnot anver's'eiy affect the'hydrate feed or he'pr' ssing 611 "surfaces may be employed, particularly those having boiling'p'oin'ts of ab'c'iut the same order as water. Further, the liquid maybe a solution, that is, it can contain vari- "ous amounts of dissolved solids,such as sodium hydroxide ofvaryi'ng concentrations, for e'x ample, Bayer plant spent f eywar t .ormh ri qu q usu ll t h ated. in e referred"heatd feedof hydrate theresult'ant a i eat he ntf 't i i tiht 'be pointed "out hereinafter, their use generally 4 will be sufiicient to raise the temperature to just below the boiling point. However, the invention includes cold hydrate feed with cold water feed where the heat generated in the compression zone is sufiicient to raise the temperature above the boiling point for ejection by flashing of the liquid to vaporon release of pressure. In fact, the sticking problem with cold hydrate feed is aggravated, and the wetting of the rolls substantially. eliminates such sticking with cold hydrate, as well as with a hot hydrate feed v I The water, preferably as a spray, maybe added to, the rolls in a number of ways such as by nozzles Qor' aIperforated pipe. However, any other suitable m'eans rhay be employed su'chas" having, the rolls 'dip intoa pan or trough containing water or by means of moistened rollers contacting the compression rollsor by a combination of these methods. It has been found best to position a spray as close to the feed point and compression zoneas possible. Regardless of the methodof application, it is essential that the amount of water be s'ufiicien t to maintainthe' rolls in a wette'dpondition until eompressionoc faces and the hydrate fmass's'urfaces.

"Instead of using r'oll type apparatus, it is entirely feasible to use stationary or'r'eciprocat ing presses. The 'die or mold surface's of the press can be moistened with tempfirature'conditions established and maintained to produce vapor at the pellet-die interface upon opening the mold. Thus, thew'etted mold is closed and the feed corn pressed at pressuress'utficient to form the pellet and producea temperatureabovesthe boiling point of the water, and the' mold is then ope'nedto obtain ejection of the pellets without sticking. The briquetting apparatusesfdescribed herein may be operated at various speeds,' pres.-

sures, etc., a s is well known in the art. Furthermore, it

iswithin the scope 'of this invention 'to utilize ,s'rrioiith rollswith nodie pockets for the purpose of fio'cculating or predensifying aluminum hydrate to reduce dust'losses 'in calcining, handling and at pot line operations, and to obtain inore'rapid heat transfer.

' "After briquetting, the briquettes are readily calcined atatemper'aturefoflabout840 F. for three hours to remove at'fleas't a' portion of the chemically bound water to providetin activated alumina containingfbriquette suitable "for use in theproduction 'of aluminum fluoride by passing HF through a bed of the briquetted material atafreacti'on temperature of from about]660'to about 1200 F. 'The temperature may be raised or lowered as desired to' remove' more or less water and the time of calcination suitably adjusted thereto such as is well known in the art. For example, the temperature ay var from' about 400 F."to about 15 0O F. or higher it dead bnrnedjrnaterialis desiredand the time from a fewrninutes'tq severaihours. Other uses of the calcined articles are as adsorbentsand/or catalysts (activated alumina), catalyst carriers, cements, and so forth.

QItis .notevivonng'aswill be'hereinafter more clearly set forth in the examples, thatfthe' briquettes produced according to thepresentinvention exhibited a, high pb e pnntheadlfiwantirpll,atthe point of eompr sion,

for example, as shown by the die, pocketsatlS. The

$ .1, *iY iTkef sr e an t smm pression was applied to rolls 11 and 12 by springs 18 and 19 held under compression through contact with stationary points 20 and 21 such as a housing not shown. Feed hopper 22 or other suitable means was provided for feeding hydrate 23 to the rolls. Spray nozzles 24 and 25 were provided for spraying the rolls prior to contacting the hydrate which nozzles were fed with water by means of pipe 26.

The alumina hydrate feed varying from 100 to 325 mesh of which about 85.4% was +325 mesh at a temperature of 200 F. was fed to hopper 22 where it fell to zone 27 defined by die pockets 13 in clockwise turning roll 11 and 14 in counterclockwise turning roll 12. As the rolls turned at about R. P. M. the hydrate was compressed at 30,000 pounds across the face of the rolls into the form of briquette 28 (almond shaped-about 1%" long x wide max. x max. thick weighing about 16 grams) by means of the compression exerted on rolls 11 and 12 respectively thru springs 18 and 19 which in turn compressed the briquette. In operation the rolls never touched because of steel spacers or shims which are installed to prevent possibility of contact. This insures the formation of a land between the pockets as shown by a small amount of hydrated alumina which entered the zone at the outer periphery between thedie pockets on the same roll as at 29 forming the land on the pellet about a minimum of ,5 thick as it discharged. This land readily broke off during subsequent handling and screening. The formed briquette was discharged from the die pockets as the die pockets separated at 30 falling to screen 31 wherein the fines including lands were recycled by suitable means indicated by line 32 and fed to hopper 22 after screening through a A" screen. A ball mill may be utilized if desired to increase the uniformity of feed. The briquettes produced by the herein described pressing operation and discharged from the screen were calcined at 840 F. to provide an activated alumina briquette.

The water added to rolls 11 and 12 through spray nozzles 24 and 25 respectively formed a film on the rolls. This film according to one theory of operation is heated by contacting the heated hydrate in die pockets 13 and 14 and is further heated by friction during the compression period at point 15. Thereafter, as the dies moved apart at the point represented by 30 the pressure was released from the water, which had been superheated by the heat generated during compression, and it flashed, thus aiding in the expulsion of the briquette from the die and eliminating sticking and breakage. It, of course, is to be understood that the invention is not to be limited in any manner by the theory herein presented, but it suflices to state that the action of the wetted pressing surfaces and a controlled temperature in the compression zone eliminates sticking and minimizes breakage while obtaining pellets of improved strength.

Additional tests were conducted which demonstrates the advantages obtained by the addition of water to the roll surfaces when bn'quetting. These tests were conducted with about 30,000 pounds pressure across the face of the rolls moving at about 5 R. P. M. Tests 1, 2, and 3 were conducted without the addition of water to the rolls. However, in test 3 water was mixed with the hydrate in the amount of 2.5/100 weight ratio of water to hydrate prior to briquctting. Test 4 is presented for comparative purposes showing the effect of spraying water on the rolls in increasing the number of whole briquettes produced free of cracks and chips as well as in eliminating the stresses in the briquettes which otherwise form. The as is breaking strength is a measure of the breaking strength prior to calcining. Calcined briquettes were heated to 842 F. for 3 hours. Tests 4 and 5 clearly show an increase in the number of whole briquettes, produced by the combination of providing a film of water and heat as compared to tests 1 and 2 wherein water was not added and test 3 wherein the hydrate feed was Table Film of Water in Compression Zone Breaking Strength (pounds) Test No.

"As is Calcined flHydrate feed mixed with water in 2.5HnOIIOOAhOzBHzO weight re 0.

! Briquette too soft to handle.

Further tests were conducted in which a lubricant was added to the hydrate feed or to the rolls. When aluminum stearate, about 0.25% by weight, was mixed with the hydrate, the resulting as is briquettes exhibited a strength of only about pounds and the proportion of whole briquettes obtained was only about 50%. With a light lubricating oil on the rolls, the results were less favorable with excessive sticking of the pellets in the die pockets.

In summary, it is apparent that the present invention teaches that new and unexpected increases in strength of briquettes and in the number of whole briquettes obtained and in the essentially complete elimination of sticking can be realized by merely maintaining a film of water on the pressing surfaces entering the compression zone and providing suflicient heat to raise the temperature of the volatile liquid above its vaporization point so that it will flash or rapidly vaporize on release of pressure to eject the briquettes. The briquettes so obtained are harder than briquettes made without the use of volatile liquid such as water. Further, the addition of expensive binders or lubricants is avoided as well as the concomitant steps and equipment necessary to insure thorough mixing and any subsequent steps required to remove the lubricant. Again, the hydrate can advantageously be fed directly to the compression zone in heated condition from the driers used for removing the mechanically held water of the precipitated and filtered aluminum hydrate. Also, as the amount of fines and broken pellets is decreased, the equipment capacity is increased by reducing recirculation of fines back to the feed.

What we claim is:

1. The method of producing shaped bodies from hydrated alumina containing material characterized by an increase in the amount of whole bodies obtained and the essentially complete elimination of sticking of the material to the pressing surfaces which comprises providing a compression zone with a volatile liquid in an amount sufficient to maintain a film on the pressing surfaces thereof, delivering particulate alumina hydrate containing material to said zone in an amount sufficient to form a briquette, compressing said surfaces to efiect formation of a briquette in said compression zone while maintaining the temperature in said zone sufiicient to heat the liquid above its atmospheric boiling point, and releasing the pressure from said surfaces to permit vaporization of said liquid and ejection of the resulting briquette.

2. The method of producing shaped bodies according to claim 1 containing the additional step of calcining the formed briquette to remove at least a portion of the water of constitution.

3. The method of producing pellets of hydrated alumina characterized by an increase in the amount of whole pellets obtained and the substantially complete elimination of sticking, comprising supplying to a compression zone water amasss,

inszanvamount sutficient to aform a film on theflpressing surfaeess ofisaid, zone, delivering az mass; of particulate: hydratedt alumina, to said zone containing said film; and:

then tcompressing said :masswhilev establishingandlmain:

tainin'g arpressure sutficienttozformadensehard pellet and a temperature-sufiieient-to produce-;steamton release.of'said pressure to eject the pellet. ,r

4. The method of producing shaped bodies from predominantly hydrated alumina containing material particularly-useful 1 in the .productionaof aluminum fluoride, characterized by anrincrease. in, the amount of whole bodies obtained and the 'substa'ntially complete eliminations of clogging, comprising supplyingjo a pressing Zone water in an amount sufiicient toiform a1 film on the pressingsurtaces of said zone, delivering atmasfs fpajrticulate predominantly hydrated alumina containing material at:a..temperature notabove' about 350 F5 to said zone while maintaining the wettedpressing surfaces en-v tering said. zone-.belowithe atmospheric. boiling point a of the water, compressing said mass, at a pressure suificient to form a dense hard briquette. and to increase the temperature above the atmospheric boilingpoint'of the'water,

opposing rolls containing diesr in ther-surfaces thereofr andrevolving in .opppsiterdirectionuto, form a compression zone ,betweenisaidcrolls, WhiChCOIIIP'IiSQS supplyingto the surfacesofsaid rollsran-amount of volatile, liquid 1 suflicientto. formia film thereon, delivering a massof particulate predominantly hydratedalumi-na containing material tot-said zonein an amountusufiicienttto form a briquette, and compressing said mass toaproduce a pres sure sufficient; to, form a.v denser hard r briquette and to establish andmaintain a temperature. insaid f zone' above the; atmosphericboiling point of said liquid.

6. A method of I producing alumina hydrate pellets which comprises maintaining afilm of Water on the press ing surfacesof; a pellet-forming. compression zone, and feeding altunina hydrate to said zone-in amount .suffi'cient toform a vpelletQand compressing thealurnina to produce pellet-forming pressure in said zones and to produce a temperature. in said zone in' excess of the. atmospheric boiling point ofiithe Water.

7.- A method accordingltoclaim 6 in which the alumina hydrater'feed isat atemperature such Vthatth'e-temperature of -the.water'on:the pressing surfacesrprior to compression in the zone-is just belowits: atmospherieboilingl point;

8'. A method according to claim '7 in which the hydrate feed is at'a temperature not exceeding about 20051 References Citedin the file of this patent UNITED 'STATES PATENTS 874,167 Crow Da 17, 1907 

6. A METHOD OF PRODUCING ALUMINA HYDRATE PELLETS WHICH COMPRISES MAINTAINING A FILM OF WATER ON THE PRESSING SURFACES OF A PELLET-FORMING COMPRESSION ZONE, AND FEEDING ALUMINA HYDRATE TO SAID ZONE IN AMOUNT SUFFICIENT TO FORM A PELLET, AND COMPRESSING THE ALUMINA TO PRODUCE PELLET-FORMING PRESSURE IN SAID ZONE AND TO PRODUCE A TEMPERATURE IN SAID ZONEIN EXCESS OF THE ATMOSPHERIC BOILING POINT OF THE WATER. 